CN112358290B - 一种铁氧体材料及其制备方法和用途 - Google Patents
一种铁氧体材料及其制备方法和用途 Download PDFInfo
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- CN112358290B CN112358290B CN202011211159.XA CN202011211159A CN112358290B CN 112358290 B CN112358290 B CN 112358290B CN 202011211159 A CN202011211159 A CN 202011211159A CN 112358290 B CN112358290 B CN 112358290B
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- ferrite material
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- 239000000463 material Substances 0.000 title claims abstract description 126
- 229910000859 α-Fe Inorganic materials 0.000 title claims abstract description 123
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 238000005245 sintering Methods 0.000 claims abstract description 53
- 238000001035 drying Methods 0.000 claims abstract description 51
- 239000000126 substance Substances 0.000 claims abstract description 23
- 239000002243 precursor Substances 0.000 claims abstract description 22
- 239000002994 raw material Substances 0.000 claims abstract description 21
- 238000002156 mixing Methods 0.000 claims abstract description 11
- 238000009740 moulding (composite fabrication) Methods 0.000 claims abstract description 11
- 238000000498 ball milling Methods 0.000 claims description 67
- 238000010438 heat treatment Methods 0.000 claims description 50
- 238000000034 method Methods 0.000 claims description 44
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 42
- 238000000227 grinding Methods 0.000 claims description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- 239000000843 powder Substances 0.000 claims description 20
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 13
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 13
- 238000000465 moulding Methods 0.000 claims description 11
- 239000003960 organic solvent Substances 0.000 claims description 11
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 10
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(iii) oxide Chemical compound O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 5
- 238000004891 communication Methods 0.000 claims description 5
- 238000000748 compression moulding Methods 0.000 claims description 5
- 239000000696 magnetic material Substances 0.000 claims description 5
- 238000003801 milling Methods 0.000 claims description 4
- 125000003158 alcohol group Chemical group 0.000 claims 2
- 150000002500 ions Chemical class 0.000 abstract description 11
- 238000004519 manufacturing process Methods 0.000 abstract description 10
- 229910052797 bismuth Inorganic materials 0.000 abstract description 5
- 229910052761 rare earth metal Inorganic materials 0.000 abstract description 4
- 150000002910 rare earth metals Chemical class 0.000 abstract description 4
- 230000000052 comparative effect Effects 0.000 description 12
- 238000005498 polishing Methods 0.000 description 5
- 238000007873 sieving Methods 0.000 description 5
- 239000002002 slurry Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000006467 substitution reaction Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 229910002971 CaTiO3 Inorganic materials 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 229910000416 bismuth oxide Inorganic materials 0.000 description 2
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000002223 garnet Substances 0.000 description 2
- 230000010354 integration Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 230000002411 adverse Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010981 drying operation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium oxide Inorganic materials O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000011656 manganese carbonate Substances 0.000 description 1
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
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Abstract
本发明提供了一种铁氧体材料及其制备方法和用途。所述铁氧体材料的化学式为Bi1.3Cax+2yY1.7‑x‑2yFe5‑x‑yZrxWyO12;所述x为0.3~0.4,所述y为0.01~1。所述制备方法包括以下步骤:(1)将铁氧体材料的原料进行混合,烧结,得到铁氧体材料的前驱体;(2)将步骤(1)所述的铁氧体材料的前驱体再次进行混合,烘干,成型,烧结,得到所述铁氧体材料。所述铁氧体材料中的Bi和Ca元素能够替代部分稀土Y元素,Zr、W元素能够替代部分Fe离子,利用它们的电磁特性和补偿点来获得合适的4πMs、ΔH和Tc等参数。同时对应的制备工艺稳定且可重复性好,适合大批量生产,大大降低了生产成本。
Description
技术领域
本发明属于微波通信领域及磁性材料领域,涉及一种铁氧体材料及其制备方法和用途。
背景技术
随着微波技术的迅猛发展,系统对元器件小型化的要求越来越迫切,而铁氧体元器件的体积远高于其他元器件,因此其小型化、轻量化的任务尤为重要。人们以前对微波铁氧体的研究多集中在材料的微波磁损耗方面,而对介电常数研究得相对较少。近年来,器件设计者对高介电常数材料,不断提出要求,特别是小线宽、高介电常数材料。于是高介电常数的石榴石材料成为了微波铁氧体研究领域中的热点之一。
现有微波铁氧体的介电常数在12~16之间,在低频环形器隔离器设计时器件尺寸偏大,无法满足小型化、集成化的需求。若提高铁氧体的介电常数到25以上,可以把隔离器环形器的尺寸缩小25%以上,达到小型化、集成化的需求。
当前4πMs=1850~1950Gs的微波铁氧体材料在5G基站环形器或隔离器的应用较为广泛。关于高介电常数的微波铁氧体材料及制造方法的专利文献已有一些。
CN107746269A公开了一种低损耗功率旋磁材料,包括以下重量份原料:Bi203的重量份数为15~20份、Y2O3的重量份数为22~26份、GeO2的重量份数为1~2.5份、CaCO3的重量份数为2~5份、Fe2O3的重量份数为41~47份、ZrO2的重量份数为2~5份、MnCO3的重量份数为0.2~1份和CaTiO3的重量份数为6~10份。但该文献的制备方法中预烧温度较高,并需额外合成CaTiO3。
US8696925B2公开了一种高介电常数石榴石铁氧体,化学式为Y2.15-2xBi0.5Ca0.35+ 2xZr0.35VxFe4.65-xO12和Bi0.9Ca0.9+2xY1.2-2xZr0.7Nb0.1VxFe4.2-xO12,其x范围分别为0~0.8和0~0.6,该文献的原料中含有带有毒性的V2O5、且预烧温度较高,生产工序复杂且对环境以及人体健康有着不利的影响。
5G通信是未来信息基础设施的重要组成部分,该技术需采用微波作为传输手段,环形器、隔离器作为不可缺少的器件,其小型化、轻量化的任务尤为重要。
如何使用一种介电常数高、△H小、Tc高以及合适的4πMs的微波铁氧体材料使得环形器隔离器小型化、集成化,是目前需要解决的一项技术问题。
发明内容
针对现有技术存在的不足,本发明的目的在于提供一种铁氧体材料及其制备方法和用途。所述铁氧体材料中的Bi和Ca元素能够替代部分稀土Y元素,Zr、W元素能够替代部分Fe离子,利用它们的电磁特性和补偿点来获得合适的4πMs、ΔH和Tc等参数,其中非磁性离子Bi3+对YIG十二面体位Y3+离子的取代,大大提高了材料的介电常数,同时会降低居里温度,而本发明合适的Bi含量可以平衡介电常数与居里温度。对应制备工艺稳定且可重复性好,适合大批量生产,大大降低了生产成本。
为达此目的,本发明采用以下技术方案:
第一方面,本发明提供一种铁氧体材料,所述铁氧体材料的化学式为Bi1.3Cax+ 2yY1.7-x-2yFe5-x-yZrxWyO12;所述x为0.3~0.4,所述y为0.01~1。
例如,所述x可以为0.3、0.32、0.34、0.35、0.38或0.4等;所述y可以为0.01、0.1、0.2、0.3、0.4、0.5、0.6、0.7、0.8或1等。
本发明中,所述铁氧体材料中的Bi和Ca元素能够替代部分稀土Y元素,Zr、W元素能够替代部分Fe离子,利用它们的电磁特性和补偿点来获得合适的4πMs、ΔH和Tc等参数,其中非磁性离子Bi3+对YIG十二面体位Y3+离子的取代,大大提高了材料的介电常数,同时会降低居里温度。
优选地,所述铁氧体材料的制备原料包括Bi2O3、CaCO3、Y2O3、Fe2O3、ZrO2和WO3。
优选地,所述Bi2O3、CaCO3、Y2O3、Fe2O3、ZrO2和WO3以如前化学式Bi1.3Cax+2yY1.7-x- 2yFe5-x-yZrxWyO12的化学计量比进行配比。
优选地,所述铁氧体材料中Bi含量为33~33.4wt%,例如33wt%、33.1wt%、33.2wt%、33.3wt%或33.4wt%等。
本发明中,所述铁氧体材料中Bi含量控制在33~33.4wt%,可以实现其介电常数在27.7左右,同时可以平衡介电常数与居里温度。
第二方面,本发明提供一种如第一方面所述的铁氧体材料的制备方法,所述制备方法包括以下步骤:
(1)将铁氧体材料的原料进行混合,烧结,得到铁氧体材料的前驱体;
(2)将步骤(1)所述的铁氧体材料的前驱体再次进行混合,烘干,成型,烧结,得到所述铁氧体材料。
本发明中所提供的制备方法,制备过程稳定且可重复性好,制备得到的铁氧体材料,有着较高的介电常数和居里温度,适合大批量生产,大大降低了生产成本。
优选地,步骤(1)所述混合的方法包括球磨。
优选地,所述球磨包括将所述铁氧体材料的原料、溶剂和磨球放入球磨罐中进行球磨。
优选地,所述溶剂包括水和/或有机溶剂。
优选地,所述有机溶剂包括酒精和/或丙酮,进一步优选为酒精。
本发明中,进一步优选为酒精的原因为酒精为有机溶剂,具有分散效果好,能促进球磨的球磨效率,减少对材料的影响。
优选地,所述磨球包括氧化锆磨球。
优选地,所述球磨的转速为50~100r/min,例如50r/min、60r/min、70r/min、80r/min、90r/min或100r/min等。
优选地,所述球磨的时间为10~20h,例如10h、11h、12h、13h、14h、15h、16h、17h、18h、19h或20h等。
优选地,步骤(1)所述烧结前先进行烘干操作。
优选地,所述烘干的温度为100~200℃,例如100℃、110℃、120℃、130℃、140℃、150℃、160℃、170℃、180℃、190℃或200℃等。
优选地,所述烘干的时间为10~20h,例如10h、11h、12h、13h、14h、15h、16h、17h、18h、19h或20h等。
优选地,步骤(1)所述烧结的升温速率为1~3℃/min,例如1℃/min、1.5℃/min、2℃/min、2.5℃/min或3℃/min等。
优选地,步骤(1)所述烧结的温度为790~830℃,例如790℃、800℃、810℃、820℃或830℃等。
优选地,所述烧结的时间为4~10h,例如4h、5h、6h、7h、8h、9h或10h等。
优选地,步骤(2)所述混合的方法包括球磨。
优选地,所述球磨包括将所述铁氧体材料的前驱体、溶剂和磨球放入球磨罐中进行球磨;
优选地,所述溶剂包括水和/或有机溶剂。
优选地,所述有机溶剂包括酒精和/或丙酮。
优选地,所述磨球包括氧化锆磨球。
优选地,所述球磨的转速为50~100r/min,例如50r/min、60r/min、70r/min、80r/min、90r/min或100r/min等。
优选地,所述球磨的时间为30~40h,例如30h、32h、34h、35h、38h或40h等。
优选地,步骤(2)所述烘干的温度为100~200℃,例如100℃、110℃、120℃、130℃、140℃、150℃、160℃、170℃、180℃、190℃或200℃等。
优选地,所述烘干的时间为10~20h,例如10h、11h、12h、13h、14h、15h、16h、17h、18h、19h或20h等。
优选地,在烘干后的粉料中加入聚乙烯醇溶液。
本发明中,聚乙烯醇起到粘结剂的作用,可以使得烘干后的粉料颗粒之间接触更紧密,利于后续的成型。
优选地,以烘干后的粉料为100%计,所述聚乙烯醇溶液的加入量为0.8~1.5%,例如0.8%、1%、1.2%或1.5%等。
优选地,步骤(2)所述成型的方法包括压制成型。
优选地,所述成型后的物质的成型密度为3.5~3.6g/cm3,例如3.5g/cm3、3.52g/cm3、3.55g/cm3、3.58g/cm3或等3.6g/cm3。
步骤(2)所述烧结包括三次升温操作,所述升温操作包括一次升温、二次升温和三次升温。
本发明中,成型后的烧结过程进行三次升温操作的原因为第一次升温主要是把毛坯内的水份蒸发和粘合剂的挥发过程,需缓缓升温,以避免水份和粘合剂的急剧挥发引起坯件开裂。第二段升温主要是毛坯逐渐收缩,坯件颗粒间发生固相反应,形成晶粒,此时升温速度可快些,第三段升温主要是了抑制Bi2O3的挥发,加快Bi离子的取代。
优选地,所述升温操作的升温速率为1.5~3.5℃/min,例如1.5℃/min、2℃/min、2.5℃/min、3℃/min或3.5℃/min等。
优选地,所述一次升温升至的温度为450~550℃,例如450℃、480℃、500℃、520℃或550℃等。
优选地,所述二次升温升至的温度为750~850℃,例如750℃、760℃、770℃、800℃、820℃、840℃或850℃等。
优选地,所述三次升温升至的温度为1020~1080℃,例如1020℃、1040℃、1050℃、1070℃或1080℃等。
优选地,所述升温后烧结的时间为6~10h,例如6h、7h、8h、9h或10h等。
作为优选的技术方案,本发明中,所述铁氧体材料的制备方法包括以下步骤:
(1)将铁氧体材料的原料、酒精和氧化锆磨球加入球磨罐中,以50~100r/min的球磨速率球磨10~20h,在烘箱中以100~200℃的烘干温度烘干10~20h,烘干后以790~830℃的烧结温度烧结4~10h,得到铁氧体材料的前驱体;
(2)将步骤(1)所述铁氧体材料的前驱体、酒精和氧化锆磨球加入球磨罐中,以50~100r/min的球磨速率球磨30~40h,在烘箱中以100~200℃的烘干温度烘干10~20h,烘干后加入聚乙烯醇溶液,进行压制成型,得到成型密度为3.5~3.6g/cm3的物质,将所述成型后的物质以1.5~3.5℃/min的升温速率升温至450~550℃,再以1.5~3.5℃/min的升温速率升温750~850℃,最后以1.5~3.5℃/min得升温速率继续升温至1020~1080℃的烧结温度烧结6~10h,得到铁氧体材料。
第三方面,本发明还提供一种如第一方面所述的铁氧体材料的用途,所述用途包括将所述铁氧体材料用于微波通信和/或作为磁性材料。
与现有技术相比,本发明具有以下有益效果:
(1)本发明提供的铁氧体材料,其中的Bi、Ca元素能够替代部分稀土Y元素,Zr、W元素能够替代部分Fe离子,利用上述元素的电磁特性和补偿点来获得合适的4πMs、ΔH和Tc,尤其是该铁氧体材料的组配方将Bi含量控制在33~33.4wt%,实现了介电常数为27.7左右,其中非磁性离子Bi3+对YIG十二面体位Y3+离子的取代,大大提高了材料的介电常数,同时会降低居里温度,而本发明合适的Bi含量可以平衡介电常数与居里温度。因此本发明所提供的铁氧体材料的4πMs=1850±50(Gs)的介电常数在28±2,△H<60(oe),居里温度>240℃,密度>5.9g/cm3。
(2)本发明提供的制备方法,制备工艺稳定且可重复性好,适合大批量生产,大大降低了生产成本。
具体实施方式
下面通过具体实施例来进一步说明本发明的技术方案。本领域技术人员应该明了,所述实施例仅仅是帮助理解本发明,不应视为对本发明的具体限制。
实施例1
本实施例提供一种铁氧体材料,所述铁氧体材料的化学式为(Bi1.3Ca0.5Y1.2Fe4.6Zr0.3W0.1O12)所述铁氧体材料的原料包括纯度为99.95%的Y2O3,纯度为99.95%的Bi2O3,纯度为99%的CaCO3,纯度为99.2%ZrO2,纯度为99.5%的Fe2O3,和纯度为99.5%的WO3。
其制备方法包括以下步骤:
(1)将按照上述化学式配比的铁氧体材料的原料、酒精和氧化锆磨球按照1000:1000:4000的重量配比加入球磨罐中,以60r/min的球磨转速球磨15小时,将球磨后的浆料放入烘箱中以120℃的烘干温度烘干16h,将烘干后的粉料过60目筛放进空气烧结炉进行预烧,以1.5℃/min的速度升温到最高预烧温度830℃,烧结6小时,得到铁氧体材料的前驱体;
(2)将步骤(1)所述铁氧体材料的前驱体、酒精和氧化锆磨球按照1000:1000:5000的重量配比为加入球磨罐中,以60r/min的球磨速率球磨32h,在烘箱中以120℃的烘干温度烘干16h,烘干后加入聚乙烯醇溶液,加入量为所述烘干粉料的质量的1.3%,用100T压机成型进行压制成型,得到成型密度为3.5g/cm3的物质,将所述成型后的物质以2℃/min的升温速率升温至500℃,再以1.66℃/min的升温速率升温至800℃,再以3℃/min继续升温至1020℃的烧结温度烧结10h,经过打磨加工,得到铁氧体材料。
实施例2
本实施例提供一种铁氧体材料,所述铁氧体材料的化学式为Bi1.3Ca0.5Y1.2Fe4.55Zr0.4W0.05O12。所述铁氧体材料的原料包括纯度为99.95%的Y2O3,纯度为99.95%的Bi2O3,纯度为99%的CaCO3,纯度为99.2%ZrO2,纯度为99.5%的Fe2O3,和纯度为99.5%的WO3。
其制备方法包括以下步骤:
(1)将按照上述化学式配比的铁氧体材料的原料、酒精和氧化锆磨球按照1000:1000:4000的重量配比加入球磨罐中,以100r/min的球磨转速球磨10小时,将球磨后的浆料放入烘箱中以180℃的烘干温度烘干12h,将烘干后的粉料过60目筛放进空气烧结炉进行预烧,以2℃/min的速度升温到最高预烧温度810℃,烧结10小时,得到铁氧体材料的前驱体;
(2)将步骤(1)所述铁氧体材料的前驱体、酒精和氧化锆磨球按照1000:1000:5000的重量配比为加入球磨罐中,以80r/min的球磨速率球磨35h,在烘箱中以150℃的烘干温度烘干15h,烘干后加入聚乙烯醇溶液,加入量为所述烘干粉料的质量的0.8%,用100T压机成型进行压制成型,得到成型密度为3.6g/cm3的物质,再将所述物质从室温以2℃/min的升温速率升温至500℃,再以1.66℃/min速率升温至800℃,最后以3℃/min继续升温至1050℃的烧结温度烧结8h,经过打磨加工,得到铁氧体材料。
实施例3
本实施例提供一种铁氧体材料,所述铁氧体材料的化学式为Bi1.3Ca0.4Y1.3Fe4.65Zr0.3W0.05O12。所述铁氧体材料的原料包括纯度为99.95%的Y2O3,纯度为99.95%的Bi2O3,纯度为99%的CaCO3,纯度为99.2%ZrO2,纯度为99.5%的Fe2O3,和纯度为99.5%的WO3。
其制备方法包括以下步骤:
(1)将按照上述化学式配比的铁氧体材料的原料、酒精和氧化锆磨球按照1000:1000:4000的重量配比加入球磨罐中,以100r/min的球磨转速球磨10小时,将球磨后的浆料放入烘箱中以180℃的烘干温度烘干12h,将烘干后的粉料过60目筛放进空气烧结炉进行预烧,以1.5℃/min的速度升温到最高预烧温度790℃,烧结6小时,得到铁氧体材料的前驱体;
(2)将步骤(1)所述铁氧体材料的前驱体、酒精和氧化锆磨球按照1000:1000:5000的重量配比为加入球磨罐中,以80r/min的球磨速率球磨35h,在烘箱中以150℃的烘干温度烘干15h,烘干后加入聚乙烯醇溶液,加入量为所述烘干粉料的质量的1%,用100T压机成型进行压制成型,得到成型密度为3.55g/cm3的物质,再将所述物质从室温以2℃/min的升温速率升温至500℃,再以1.66℃/min速率升温至800℃,最后以3℃/min继续升温至1080℃的烧结温度烧结6h,经过打磨加工,得到铁氧体材料。
实施例4
本实施例与实施例1区别为,步骤(2)中升温后的烧结温度为1000℃,其余制备方法与参数与实施例1保持一致。
实施例5
本实施例与实施例1区别为,步骤(2)中升温后的烧结温度为1100℃。
其余制备方法与参数与实施例1保持一致。
实施例6
本实施例与实施例1的区别为本实施例步骤(2)中升温后的烧结时间为25h。
其余制备方法与参数与实施例1保持一致。
实施例7
本实施例与实施例1的区别为本实施例步骤(2)中升温后的烧结时间为3h。
其余制备方法与参数与实施例1保持一致。
对比例1
本对比例提供一种铁氧体材料,所述铁氧体材料的化学式为Bi1.3Ca0.3Y1.4Fe4.7Zr0.3O12。所述铁氧体材料的原料包括纯度为99.95%的Y2O3,纯度为99.95%的Bi2O3,纯度为99%的CaCO3,纯度为99.2%ZrO2,纯度为99.5%的Fe2O3。
其制备方法包括以下步骤:
(1)将按照上述化学式配比的铁氧体材料的原料、酒精和氧化锆磨球按照1000:1000:4000的重量配比加入球磨罐中,以60r/min的球磨转速球磨15小时,将球磨后的浆料放入烘箱中以120℃的烘干温度烘干16h,将烘干后的粉料过60目筛放进空气烧结炉进行预烧,以1.5℃/min的速度升温到最高预烧温度830℃,烧结6小时,得到铁氧体材料的前驱体;
(2)将步骤(1)所述铁氧体材料的前驱体、酒精和氧化锆磨球按照1000:1000:5000的重量配比为加入球磨罐中,以60r/min的球磨速率球磨32h,在烘箱中以120℃的烘干温度烘干16h,烘干后加入聚乙烯醇溶液,加入量为所述烘干粉料的质量的1.3%,用100T压机成型进行压制成型,得到成型密度为3.5g/cm3的物质,将所述成型后的物质以2℃/min的升温速率升温至500℃,再以1.66℃/min的升温速率升温至800℃,再以3℃/min继续升温至1020℃的烧结温度烧结10h,经过打磨加工,得到铁氧体材料。
对比例2
本对比例提供一种铁氧体材料,所述铁氧体材料的化学式为Bi1.3Ca0.9Y1.0Fe4.4Zr0.5W0.1O12。所述铁氧体材料的原料包括纯度为99.95%的Y2O3,纯度为99.95%的Bi2O3,纯度为99%的CaCO3,纯度为99.2%ZrO2,纯度为99.5%的Fe2O3,和纯度为99.5%的WO3。
其制备方法包括以下步骤:
(1)将按照上述化学式配比的铁氧体材料的原料、酒精和氧化锆磨球按照1000:1000:4000的重量配比加入球磨罐中,以60r/min的球磨转速球磨15小时,将球磨后的浆料放入烘箱中以120℃的烘干温度烘干16h,将烘干后的粉料过60目筛放进空气烧结炉进行预烧,以1.5℃/min的速度升温到最高预烧温度830℃,烧结6小时,得到铁氧体材料的前驱体;
(2)将步骤(1)所述铁氧体材料的前驱体、酒精和氧化锆磨球按照1000:1000:5000的重量配比为加入球磨罐中,以60r/min的球磨速率球磨32h,在烘箱中以120℃的烘干温度烘干16h,烘干后加入聚乙烯醇溶液,加入量为所述烘干粉料的质量的1.3%,用100T压机成型进行压制成型,得到成型密度为3.5g/cm3的物质,将所述成型后的物质以2℃/min的升温速率升温至500℃,再以1.66℃/min的升温速率升温至800℃,再以3℃/min继续升温至1020℃的烧结温度烧结10h,经过打磨加工,得到铁氧体材料。
用排水法测试实施例1-7与对比例1-2制备得到的铁氧体材料的密度。
将实施例1-7与对比例1-2制备得到的铁氧体材料加工成Φ1.6×22的细棒测试其介电常数ε。
将实施例1-7与对比例1-2制备得到的铁氧体材料抛光成Φ1圆球测试△H。
将实施例1-7与对比例1-2制备得到的铁氧体材料加工成Φ2.5mm圆球测试4πMs和居里温度Tc。
表1为对实施例1-7与对比例1-2制备得到的铁氧体材料进行上述测试后的结果汇总。
表1
从以上所述的具体实施例及对比例数据分析,不同W2O3及ZrO2比例及烧结温度及保温时间对材料的4πMs、线宽及烧结密度有很大的影响。
从实施例1与实施例4-5的数据结果可知,烧结过程中温度过低,晶粒没有长大,密度低,导致线宽高;烧结温度过高会导致氧化铋的析出,也会使得密度降低,线宽恶化。
从实施例1与实施例6-7的数据结果可知,烧结过程中烧结时间过长,容易导致氧化铋的析出,造成密度低,线宽恶化;烧结时间过短会导致晶粒长不大,仍会造成密度低,线宽高。
从实施例1与对比例1的数据结果可知,铁氧体材料中不含W元素时,其结果会线宽偏高。
从实施例1与对比例2的数据结果可知,铁氧体材料中Zr元素含量过多时会导致4πMS降低,线宽恶化。
综上可以看出,本发明中所提供的铁氧体材料,其可以更好地平衡介电常数与居里温度,并具有线宽小、Tc高以及合适的4πMs的特点,能够更好地应用于微波通信或作为磁性材料。
以上所述的具体实施例,对本发明的目的、技术方案和有益效果进行了进一步详细说明,所应理解的是,以上所述仅为本发明的具体实施例而已,并不用于限制本发明,凡在本发明的精神和原则之内,所做的任何修改、等同替换、改进等,均应包含在本发明的保护范围之内。
Claims (40)
1.一种铁氧体材料,其特征在于,所述铁氧体材料的化学式为Bi1.3Cax+2yY1.7-x-2yFe5-x- yZrxWyO12;所述x为0.3~0.4,所述y为0.01~1,所述铁氧体材料中Bi含量为33~33.4wt%。
2.根据权利要求1所述的铁氧体材料,其特征在于,所述铁氧体材料的制备原料包括Bi2O3、CaCO3、Y2O3、Fe2O3、ZrO2和WO3。
3.根据权利要求2所述的铁氧体材料,其特征在于,所述Bi2O3、CaCO3、Y2O3、Fe2O3、ZrO2和WO3以化学式Bi1.3Cax+2yY1.7-x-2yFe5-x-yZrxWyO12的化学计量比进行配比。
4.根据权利要求1-3任一项所述的铁氧体材料的制备方法,其特征在于,所述制备方法包括以下步骤:
(1)将铁氧体材料的原料进行混合,烧结,得到铁氧体材料的前驱体;
(2)将步骤(1)所述的铁氧体材料的前驱体再次进行混合,烘干,成型,烧结,得到所述铁氧体材料。
5.根据权利要求4所述的铁氧体材料的制备方法,其特征在于,步骤(1)所述混合的方法包括球磨。
6.根据权利要求5所述的铁氧体材料的制备方法,其特征在于,所述球磨包括将所述铁氧体材料的原料、溶剂和磨球放入球磨罐中进行球磨。
7.根据权利要求6所述的铁氧体材料的制备方法,其特征在于,所述溶剂包括水和/或有机溶剂。
8.根据权利要求7所述的铁氧体材料的制备方法,其特征在于,所述有机溶剂包括酒精和/或丙酮。
9.根据权利要求8所述的铁氧体材料的制备方法,其特征在于,所述有机溶剂为酒精。
10.根据权利要求6所述的铁氧体材料的制备方法,其特征在于,所述磨球包括氧化锆磨球。
11.根据权利要求5所述的铁氧体材料的制备方法,其特征在于,所述球磨的转速为50~100r/min。
12.根据权利要求5所述的铁氧体材料的制备方法,其特征在于,所述球磨的时间为10~20h。
13.根据权利要求4所述的铁氧体材料的制备方法,其特征在于,步骤(1)所述烧结前先进行烘干操作。
14.根据权利要求13所述的铁氧体材料的制备方法,其特征在于,所述烘干的温度为100~200℃。
15.根据权利要求13所述的铁氧体材料的制备方法,其特征在于,所述烘干的时间为10~20h。
16.根据权利要求4所述的铁氧体材料的制备方法,其特征在于,步骤(1)所述烧结的升温速率为1~3℃/min。
17.根据权利要求4所述的铁氧体材料的制备方法,其特征在于,步骤(1)所述烧结的温度为790~830℃。
18.根据权利要求4所述的铁氧体材料的制备方法,其特征在于,所述烧结的时间为4~10h。
19.根据权利要求4所述的铁氧体材料的制备方法,其特征在于,步骤(2)所述混合的方法包括球磨。
20.根据权利要求19所述的铁氧体材料的制备方法,其特征在于,所述球磨包括将所述铁氧体材料的前驱体、溶剂和磨球放入球磨罐中进行球磨。
21.根据权利要求20所述的铁氧体材料的制备方法,其特征在于,所述溶剂包括水和/或有机溶剂。
22.根据权利要求21所述的铁氧体材料的制备方法,其特征在于,所述有机溶剂包括酒精和/或丙酮。
23.根据权利要求22所述的铁氧体材料的制备方法,其特征在于,所述有机溶剂为酒精。
24.根据权利要求20所述的铁氧体材料的制备方法,其特征在于,所述磨球包括氧化锆磨球。
25.根据权利要求19所述的铁氧体材料的制备方法,其特征在于,所述球磨的转速为50~100r/min。
26.根据权利要求19所述的铁氧体材料的制备方法,其特征在于,所述球磨的时间为30~40h。
27.根据权利要求4所述的铁氧体材料的制备方法,其特征在于,步骤(2)所述烘干的温度为100~200℃。
28.根据权利要求4所述的铁氧体材料的制备方法,其特征在于,所述烘干的时间为10~20h。
29.根据权利要求4所述的铁氧体材料的制备方法,其特征在于,在烘干后的粉料中加入聚乙烯醇溶液。
30.根据权利要求29所述的铁氧体材料的制备方法,其特征在于,以烘干后的粉料为100%计,所述聚乙烯醇溶液的加入量为0.8~1.5%。
31.根据权利要求4所述的铁氧体材料的制备方法,其特征在于,步骤(2)所述成型的方法包括压制成型。
32.根据权利要求4所述的铁氧体材料的制备方法,其特征在于,所述成型后的物质的成型密度为3.5~3.6g/cm3。
33.根据权利要求4所述的铁氧体材料的制备方法,其特征在于,步骤(2)所述烧结包括三次升温操作,所述升温操作包括一次升温、二次升温和三次升温。
34.根据权利要求33所述的铁氧体材料的制备方法,其特征在于,所述升温操作的升温速率为1.5~3.5℃/min。
35.根据权利要求33所述的铁氧体材料的制备方法,其特征在于,所述一次升温升至的温度为450~550℃。
36.根据权利要求33所述的铁氧体材料的制备方法,其特征在于,所述二次升温升至的温度为750~850℃。
37.根据权利要求33所述的铁氧体材料的制备方法,其特征在于,所述三次升温升至的温度为1020~1080℃。
38.根据权利要求33所述的铁氧体材料的制备方法,其特征在于,所述升温后烧结的时间为6~10h。
39.根据权利要求4所述的铁氧体材料的制备方法,其特征在于,所述制备方法包括以下步骤:
(1)将铁氧体材料的原料、酒精和氧化锆磨球加入球磨罐中,以50~100r/min的球磨速率球磨10~20h,在烘箱中以100~200℃的烘干温度烘干10~20h,烘干后以790~830℃的烧结温度烧结4~10h,得到铁氧体材料的前驱体;
(2)将步骤(1)所述铁氧体材料的前驱体、酒精和氧化锆磨球加入球磨罐中,以50~100r/min的球磨速率球磨30~40h,在烘箱中以100~200℃的烘干温度烘干10~20h,烘干后加入聚乙烯醇溶液,进行压制成型,得到成型密度为3.5~3.6g/cm3的物质,将所述成型后的物质以1.5~3.5℃/min的升温速率升温至450~550℃,再以1.5~3.5℃/min的升温速率升温750~850℃,最后以1.5~3.5℃/min得升温速率继续升温至1020~1080℃的烧结温度烧结6~10h,得到铁氧体材料。
40.一种如权利要求1-3任一项所述的铁氧体材料的用途,其特征在于,所述用途包括将所述铁氧体材料用于微波通信和/或作为磁性材料。
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CN115340371B (zh) * | 2022-07-26 | 2023-07-21 | 深圳顺络电子股份有限公司 | 一种铁氧体材料、制备方法及微波通信器件 |
CN115331907B (zh) * | 2022-09-01 | 2023-11-21 | 南京金宁微波有限公司 | 一种应用于大功率微波器件的旋磁铁氧体材料及其制备方法 |
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US9527776B2 (en) * | 2010-11-30 | 2016-12-27 | Skyworks Solutions, Inc. | Effective substitutions for rare earth metals in compositions and materials for electronic applications |
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US9552917B2 (en) * | 2013-09-20 | 2017-01-24 | Skyworks Solutions, Inc. | Materials, devices and methods related to below-resonance radio-frequency circulators and isolators |
US10181632B2 (en) * | 2013-12-18 | 2019-01-15 | Skyworks Solutions, Inc. | Tunable resonators using high dielectric constant ferrite rods |
US9771304B2 (en) * | 2015-06-15 | 2017-09-26 | Skyworks Solutions, Inc. | Ultra-high dielectric constant garnet |
CN105174934A (zh) * | 2015-08-31 | 2015-12-23 | 天长市中德电子有限公司 | 一种高饱和磁感应强度宽温低损耗软磁铁氧体的制备方法 |
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